CN1030459C - Composition of thermoplastic resin - Google Patents
Composition of thermoplastic resin Download PDFInfo
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- CN1030459C CN1030459C CN87107381A CN87107381A CN1030459C CN 1030459 C CN1030459 C CN 1030459C CN 87107381 A CN87107381 A CN 87107381A CN 87107381 A CN87107381 A CN 87107381A CN 1030459 C CN1030459 C CN 1030459C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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Abstract
In the case where a polyamide is blended with a specific partially crosslinked graft-modified polyolefin elastomer obtained by dynamically heat-treating a blend of a peroxide-crosslinking olefin copolymer rubber and an olefinic plastic with an unsaturated carboxylic acid or derivative thereof, an unsaturated epoxy monomer or an unsaturated hydroxy monomer in the presence of an organic peroxide, if the graft-modified polyolefin plastomer occupies a major portion, a composition strength and the resistance against heat agin is obtained and if the polyamide occupies a major portion, a composition excellent in the impact resistance, the rigidity and the tensile strength is obtained.
Description
The invention belongs to the composition of forming by graft-modified polyolefin based elastomers and polymeric amide.Furtherly, be about mixture with peroxide crosslinking type ethylene series interpolymer rubber and olefin series plastic, with unsaturated carboxylic acid or derivatives thereof, unsaturated epoxy monomer or unsaturated carboxylic monomer, under the condition that organo-peroxide exists, carry out dynamic thermal treatment, again this has been carried out partial cross-linked graft-modified polyolefin based elastomers (a) and polymeric amide (b) and carried out resulting resin combination after the blend.
Thermoplastic elastomer has been widely used for making trolley part (corrugated tube, tube, interior dress sheet material, splash pan etc.) industrial machinery part (pressure piping, seal washer, barrier film etc.), electric mechanical part and material of construction etc. as the surrogate of elastomerics, the particularly vulcanized rubber of saving the energy, saving resource-type.
By the crystalline thermoplastic polyolefin-based resins with add the composition for thermoplastic elastomer that sulphur ethylene, propylene polyenoid interpolymer rubber is formed, all on the books on special public clear 58-46138 communique of Japanese Patent and the public clear 55-18448 communique of spy.The shortcoming of this composition is caoutchouc elasticity and physical strength imbalance.
In addition, by crosslinked ethylene, propylene polyenoid interpolymer rubber, acrylonitrile butadiene interpolymer rubber and acrylic resin, the composition for thermoplastic elastomer that nylon resin is formed is on the books on No. 4338413 communique of United States Patent (USP).Though this composition has oil-proofness and all other characteristics, it has the critical defect of heat-resistant aging difference and weathering resistance difference.
Also have, open on the clear 57-8246 communique on the books the Japanese Patent spy by the composition that the unsaturated carboxylic acid-modified thing of α, β and the polymeric amide of polyolefin resin and ethylene alpha-olefin interpolymers mixture are formed.Though this composition has higher physical strength, as thermoplastic elastomer, it but lack its one of the key property that should possess-flexibility.
According to above-mentioned, a kind of composition for thermoplastic elastomer with good oil-proofness, high mechanical strength and good heat-resistant aging still belongs to unknown at present.
In addition, polyamide resin has been subjected to attracting attention of people because of the rerum natura of the excellence that it had as engineering plastics.But the performances such as low-temperature impact resistance, water tolerance and resistance to salt water that can't say it are just very abundant, and it is still waiting further perfect.
Modified alphas such as ethylene alpha-olefin interpolymers-ethylene series elastomeric polymer that polyamide resin and α, beta-unsaturated carboxylic acid are carried out forming after the grafting mixes and as the method for raising Emhorn shock strength, all on the books in following prior art file, example: the special public clear 42-12546 communique of Japanese Patent, special public clear 55-44108 communique, spy open clear 55-9661 communique, the spy opens clear 55-9962 communique etc.Disclosed all compositions all interosculate in these prior art files, and promptly as long as improve shock-resistance such as its Emhorn shock strength, then its rigidity just can decline to a great extent, even and the drop impact under the low temperature also undesirable.Use these compositions, be difficult to make not only have high rigidity, but also actual moulded products with higher shock-resistant characteristic.In addition, these compositions are poor excessively because of its melt fluidity toward contact, so its processing forming is relatively poor.
Open the Japanese Patent spy and to disclose a kind of composition of eliminating above-mentioned defective in the clear 59-147008 communique, that is having good shock-resistance and high inflexible Amilan polyamide resin composition concurrently, it is by carrying out composition that the modified polyolefin that grafting after generate and polyamide resin form at the ethylene alpha-olefin interpolymers below 35% with the unsaturated carboxylic acid or derivatives thereof in resulting under the effect of specific polymerizing catalyst, degree of crystallinity.Even but adopted this specific modified polyolefin of being put down in writing on the communique, the raising of its rigidity and tensile strength is yet unsatisfactory.
Characteristics of the present invention are that the blend that contains peroxide crosslinking type ethylene series interpolymer rubber, olefin series plastic and unsaturated carboxylic acid or derivatives thereof, unsaturated epoxy monomer or unsaturated carboxylic monomer is heat-treated under the condition that organo-peroxide exists, again this is carried out partial cross-linked, specific graft-modified polyolefin based elastomers and polymeric amide and carried out blend, when being main body, can obtain the not only composition of the good oil-proofness of tool, high mechanical strength but also the good heat-resistant aging of tool with this graft-modified polyolefin based elastomers; When being main body, then can obtaining having shock-resistance, have high rigidity and high-tensile composition again with the polymeric amide.
Furtherly, thermoplastic resin composition's of the present invention principal character is: it contains
(ⅰ) peroxide crosslinking type ethylene series interpolymer rubber 100～10 parts by weight,
(ⅱ) olefin series plastic 0～90 parts by weight [here, selected (ⅰ)+(ⅱ) be 100 parts by weight],
(ⅲ) blend of unsaturated carboxylic acid or derivatives thereof, unsaturated epoxy monomer or unsaturated carboxylic monomer 0.01～10 parts by weight carries out dynamic thermal treatment in the presence of organo-peroxide, this has been carried out partial cross-linked graft-modified polyolefin based elastomers (a) and polymeric amide (b) again and has mixed;
Thermoplastic resin composition of the present invention also can mix with following ratio: graft-modified polyolefin based elastomers (a) content for greater than 50～95, polymeric amide (b) content is 5～less than the 50(weight basis);
Thermoplastic resin composition of the present invention can also mix with following ratio: the content of graft-modified polyolefin based elastomers (a) is 5～50, polymeric amide (b) content is 5～less than the 50(weight basis);
Thermoplastic resin composition of the present invention also comprises contains following composition and content, that is: set in this graft-modified polyolefin based elastomers (a) (ⅰ) and (ⅱ) when component content adds up to 100 parts by weight, also contain:
(ⅳ) superoxide non-crosslinked type rubber-like substance 0～100 parts by weight and/or
(V) mineral oil softener 0～200 parts by weight.
That is, thermoplastic resin composition's of the present invention notable feature is: with the elastomeric composition of polymeric amide blended be under the condition that organo-peroxide exists, the blend of peroxide crosslinking type ethylene series interpolymer rubber and olefin series plastic is resulting after unsaturated carboxylic acid or derivatives thereof, unsaturated epoxy monomer or unsaturated carboxylic monomer carry out dynamic thermal treatment, carried out on the partial cross-linked graft-modified polyolefin based elastomers this point.
Therefore, resin combination of the present invention is when being main body with the elastomerics composition, and it had not only had the good heat-resistant aging of good oil-proofness, high mechanical strength but also tool; When being main body with the polymeric amide composition, it had not only had shock-resistance but also the high rigidity of tool, good fluidity and a thermotolerance.
Ideal embodiment of the present invention is as follows: when the present composition is main body with the modified polyolefin based elastomers, partial cross-linked ethylene series interpolymer rubber and olefin series plastic (preferably peroxide breakdown type olefin series plastic) form because composition (a) modified polyolefin based elastomers is by having carried out, so it has been kept good flowability, thermotolerance and heat-resistant aging and has had the elasticity of rubber.
Composition (b) polymeric amide has good oil-proofness and temperature flowing, therefore makes elastic composition maintain certain oil resistance and machine-shaping property.
Why composition for thermoplastic elastomer of the present invention can give play to the advantage of composition (a) and composition (b) fully, be because composition (a) is to carry out even modification with being easy to carry out physics, chemically combined unsaturated carboxylic acid or derivative, unsaturated epoxy monomer or unsaturated carboxylic monomer with composition (b), and this situation is as comparing with unmodified composition (a) or the situation that is added with the 3rd kind of composition of chain that can mix with composition (a) or composition (b), and its coblended interface has been strengthened greatly.
In view of above-mentioned, because the effect of above-mentioned each composition, the present embodiment provides the not only good oil-proofness of tool, but also the thermoplastic resin of high mechanical strength and good heat-resistant aging has been arranged.
In addition, when being main body with the polymeric amide, composition (a) modified polyolefin based elastomers has played and has made composition of the present invention have good shock-resistance, flowability and stable on heating effect.
Composition (b) polymeric amide has then played the effect that makes composition of the present invention have high rigidity, good heat resistance and temperature flowing.
Therefore, in this case, because the effect of above-mentioned various compositions, the present embodiment provides a kind of not only high rigidity of tool, high impact strength but also has had good mobile and stable on heating thermoplastic resin composition.
(ⅰ) peroxide crosslinking type ethylene series interpolymer rubber
Used peroxide crosslinking type ethylene series interpolymer rubber is to be the unformed elasticity interpolymer of main component such as ethylene propylene copolymer rubber, ethylene, propylene non-conjugated diene rubber, ethene butadiene copolymer body rubber, with alkene among the present invention, by mixing with organo-peroxide and under heating state, mediating, make it to be cross-linked into mobile difference or do not have mobile rubber.In addition, so-called non-conjugated diene is meant Dicyclopentadiene (DCPD), 1,4-hexadiene, two cyclooctadiene, methene norbornene, ethylidene norbornene etc.
Interpolymer rubber among the present invention, the most handy ethylene propylene copolymer rubber, ethylene, propylene non-conjugated diene rubber; Ethene is 50/50～90/10 with the ratio (ethylene/propene) of the mol of propylene repeating unit, preferably 55/45～85/15; Therein ethylene propylene non-conjugated diene interpolymer rubber, particularly ethylene, propylene 5-ethylidene-2-norbornene copolymer rubber and ethylene, propylene 5-ethylidene-2-norbornene Dicyclopentadiene (DCPD) tetrapolymer more help obtaining having good heat resistance, high stretch and elastic thermoplastic elastomer.
In addition, the mooney viscosity ML of interpolymer rubber
1+4(100 ℃) are 10～250, preferably 40～150.Viscosity is as less than 10, and the shock strength of composition then can reduce; But viscosity is as greater than 250, and the flowability of composition then can variation.
Also have, the iodine number of interpolymer rubber (degree of unsaturation) is preferably in below 25, can obtain flowability and impact strength in this scope: the equilibrated resin combination.
(ⅱ) olefin series plastic
Olefin series plastic of the present invention is that one or more the monomer alkene that obtains with high-pressure process or low-pressure process carries out polymerization and the crystalline polymer solid resultant that generates.
This resinoid can be enumerated: the homopolymer or the copolymer resin of the monomer alkene of isotactic polymer and syndiotactic polymer, these representational materials are all available on market.
The ideal olefin feedstock can be exemplified below: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 2-methyl isophthalic acid-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, 1-octene, 1-decene and the above-mentioned mixture of alkene more than two kinds.The polymeric mode no matter be random polymerization or block polymerization, just can adopt so long as can obtain resinous substance.
Wherein, the ideal olefin series plastic is the olefin series plastic and the polyethylene of peroxide breakdown type.
So-called peroxide breakdown type olefin series plastic is meant by mixing with superoxide among the present invention, under heating condition, knead, make the olefin series plastic of its decrease in molecular weight, Resin Flow increase because of thermolysis, for example can enumerate: the multipolymer of isotatic polypropylene and propylene etc. and other a small amount of alpha-olefins, as: propylene ethylene copolymers, propylene butene-1 copolymer, propylene 1-hervene copolymer body, propylene 4-methyl-1-pentene interpolymer etc.The melting index of mixed olefin series plastic (ASTM-D-1238-65T, 230 ℃) is 0.1-5.0, is preferably in 5～20 scope.Olefin series plastic of the present invention has the mobile and stable on heating effect that can improve composition.
(ⅲ) unsaturated carboxylic acid or derivatives thereof, unsaturated epoxy monomer or unsaturated carboxylic monomer
The α, the β unsaturated carboxylic acid or derivatives thereof that are adopted as one of composition of the present invention (ⅲ), can enumerate as follows particularly: vinylformic acid, methacrylic acid, maleic acid, FUMARIC ACID TECH GRADE, methylene-succinic acid, methyl-maleic acid, tetrahydrofuran (THF) acid, two rings (2,2,1) hept-2-ene"-5, unsaturated carboxylic acids such as 6-dicarboxylic acid; MALEIC ANHYDRIDE, methylene-succinic acid bar, methyl maleic anhydride, tetrahydrofuran (THF) acid bar, two ring (2,2,1) hept-2-ene"s-5, unsaturated carboxylic acid bars such as 6-dicarboxylic anhydride; Methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl cis-butenedioic acid, diethyl fumarate, methylene-succinic acid dimethyl ester, methyl-maleic acid diethyl ester, tetrahydrobenzene two dimethyl phthalates, two rings (2,2,1) hept-2-ene"-5, the ester of unsaturated carboxylic acids such as 6-dimethyl dicarboxylate etc.It would be desirable maleic acid, two ring [2,2,1] hept-2-ene"-5,6-dicarboxylic acid or their acid anhydrides in the above-mentioned substance.
In addition, the another kind of unsaturated epoxy monomer that is divided into (ⅲ) as the present invention, only is some following materials, for example: the glycidyl ester of the unsaturated monocarboxylic acid of glycidyl acrylate, glycidyl methacrylate, right-vinylbenzene carboxylic acid glycidyl ester etc.; Maleic acid, methylene-succinic acid, methyl-maleic acid, butylene tricarboxylic acid, bridge-suitable-dicyclo (2,2,1) heptan-5-alkene-2,3-dicarboxylic acid, bridge-suitable-dicyclo (2,2,1) heptan-5-alkene-2-methyl-2, single glycidyl ester or many glycidyl esters of unsaturated polyprotonic acids such as 3-dicarboxylic acid; Allyl glycidol ether, 2-methacrylic glycidyl ethyl ether, neighbour-allyl phenyl glycidyl ether ,-allyl phenyl glycidyl ether, right-the allyl phenyl glycidyl ether, pseudoallyl phenyl glycidyl ether, neighbour-ethenylphenyl glycidyl ether ,-the unsaturated glycidyl ether of ethenylphenyl glycidyl ether, right-ethenylphenyl glycidyl ether etc.; 2-(neighbour-ethenylphenyl) oxyethane, 2-(is right-ethenylphenyl) and oxyethane, 2-(neighbour-ethenylphenyl) propylene oxide, 2-(is right-ethenylphenyl) and propylene oxide, 2-(neighbour-allyl phenyl) oxyethane, 2-(is right-allyl phenyl) and oxyethane, 2-(neighbour-allyl phenyl) propylene oxide, 2-(is right-allyl phenyl) and propylene oxide, right-Racemic glycidol vinylbenzene, 3,4-epoxy-1-butylene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-hexene, 3,4-epoxy-3-methyl isophthalic acid-hexene, 5,6-epoxy-1-hexene, the single oxide compound of vinyl cyclohexene, allyl group-2,3-oxirane ring amyl ether etc.
Also have, unsaturated carboxylic monomer as one of composition among the present invention (ⅲ), can enumerate a following monomer above ethylene unsaturated bond and hydroxyl that contains, for example: Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, poly-second two glycol monomethacrylates, polypropylene glycol monomethacrylate etc., particularly hydroxyethyl methylacrylate and Rocryl 410 are comparatively ideal.
More than these are divided into (ⅲ) when carrying out the described dynamic thermal treatment in back, being taken as the graft modification agent uses, it has the effect of the mixed interface of strengthening polymeric amide and graft-modified polyolefin based elastomers, and it can also improve the shock-resistance of Amilan polyamide resin composition.
Graft-modified polyolefin based elastomers of the present invention also can contain (ⅳ) superoxide non-crosslinked type rubber-like substance and/or (V) mineral oil softener.
(ⅳ) superoxide non-crosslinked type rubber-like substance
The so-called superoxide non-crosslinked type rubber-like substance of this composition (ⅳ) is meant such as polyisobutene, isoprene-isobutylene rubber (II R), to contain propylene be that propylene ethylene copolymers rubber, material the Atactic Polypropelene and superoxide more than 70 moles mixes, under heating condition, knead the neither crosslinked and also undiminished hydrocarbon rubber shape of its flowability material.This wherein, polyisobutene and isoprene-isobutylene rubber (II R) performance and the operation on all be optimal.
This composition can be used to improve the shock-resistance and the mobile material of Amilan polyamide resin composition, and particularly its mooney viscosity is preferably in below 60.
(V) mineral oil softener
This composition (V) mineral oil softener normally adds man-hour and the high point petroleum cut that adds in the roll-in of carrying out rubber, its application target is for the Intermolecular Forces that weakens rubber, makes rubber be easy to processing, help the dispersion of the carbon black that adds as weighting agent and white carbon black etc. simultaneously, and can reduce the hardness of vulcanized rubber, the flexibility and the elasticity of increase rubber, it can be divided into paraffinic hydrocarbons, naphthenic hydrocarbon and aromatic series etc.
Graft-modified polyolefin based elastomers (a)
Graft-modified polyolefin based elastomers of the present invention (a) is with aforesaid (ⅰ) peroxide crosslinking type olefin copolymer rubber 100～10 parts by weight, comparatively ideal is 95～10 parts by weight, it would be desirable 95～60 parts by weight, (ⅱ) olefin series plastic 0～90 parts by weight, comparatively ideal is 5～90 parts by weight, it would be desirable 5～40 parts by weight (here, selected (a)+(b) is 100 parts by weight) and (ⅲ) unsaturated carboxylic acid or derivatives thereof, the umber of unsaturated epoxy monomer or unsaturated carboxylic monomer 0.01～10 weight, preferably 0.1～5 parts by weight carry out blend, carry out dynamic thermal treatment and carry out partial cross-linked obtaining under the condition that organo-peroxide exists.
In foregoing scope, use the interpolymer rubber of composition (ⅰ), can obtain all excellent composition of rigidity, flowability, thermotolerance and shock-resistance.
Olefin series plastic with composition (ⅱ) in foregoing scope mixes, and can obtain all excellent composition of shock-resistance, flowability and formability.
In foregoing scope, use the unsaturated carboxylic acid or derivatives thereof of composition (ⅲ), unsaturated epoxy monomer or unsaturated carboxylic monomer, can obtain shock-resistance and mobile all excellent composition.
In addition, when above-mentioned each composition of the present invention is mixed, preferably add aforesaid composition (ⅳ) and (V), and the add-on that is divided into the superoxide non-crosslinked type rubber-like substance of (ⅳ) be 0～100 parts by weight, comparatively ideal be 5～100 parts by weight, the most desirable be 5～50 parts by weight; The add-on of the mineral oil softener of composition (V) be 0～200 parts by weight, comparatively ideal be 3～100 parts by weight, the most desirable be 5～80 parts by weight.
In addition, in the shock-resistance that does not influence the resin combination that to make, under the prerequisite of mobile (formability), can add weighting agent, as: lime carbonate, Calucium Silicate powder, clay, kaolin, talcum powder, silicon-dioxide, diatomite, mica powder, asbestos, alumina, barium sulfate, Tai-Ace S 150, calcium sulfate, magnesium basic carbonate, molybdenumdisulphide, graphite, glass fibre, granulated glass sphere, silica bead, charcoal fiber etc., or the adding tinting material, as: carbon black, titanium oxide, zinc oxide, colcother, ultramarine, general Lu Shi orchid, azo pigment, nitroso pigments, pigment lake, the blue or green pigment of phthalein etc.
In the present invention, according to the usage quantity in olefin series plastic or olefin copolymer rubber, can also allocate lubricant into as the stablizer of phenol system, sulphite system, phenyl chain methane series, phosphatization system or amine system and so on and known heat-resisting stabilizing agent, protective agent, weather stablizer, antistatic agent, metallic soap, wax etc.
Among the present invention, above-mentioned each mixture of ingredients under the condition that organo-peroxide exists, is carried out dynamic thermal treatment and carried out the partial cross-linked modified polyolefin based elastomers (a) of making.
So-called dynamically thermal treatment is meant under molten state and kneads.
Organo-peroxide used among the present invention can be enumerated as follows, for example: dicumyl peroxide, peroxidation two-uncle-butane, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3,1, two (tert-butyl peroxide sec.-propyl) benzene of 3-, 1, two (tert-butyl peroxide)-3 of 1-, 3, the 5-trimethyl-cyclohexane, just-butyl-4, two (tert-butyl peroxide) valerates of 4-, benzoyl peroxide, chloro benzoyl peroxide, peroxidation 2,4 dichloro benzene formyl, tert-butyl peroxide benzoate, TBPB tertiary butyl perbenzoate, tert-butyl peroxy isopropyl carbonate, diacetyl peroxide, the dodecanoyl superoxide, tert-butyl peroxide isopropyl benzene etc.
In above-mentioned these materials, stink and early stage sulfuration stable aspect, more satisfactory is: 2, and 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3,1, two (tert-butyl peroxide sec.-propyl) benzene, 1 of 3-, two (tert-butyl peroxide)-3 of 1-, 3,5-trimethyl-cyclohexane and just-butyl-4, two (tert-butyl peroxide) valerates of 4-; This wherein belongs to 1 again, and two (tert-butyl peroxide sec.-propyl) benzene of 3-are ideal.
The use level of organo-peroxide is equivalent to (ⅱ) the 0.05-3 weight percent of (ⅲ) total weight of composition (ⅰ), preferably is selected in the scope of 0.1-1 weight percent.If the use level of organo-peroxide is selected in this scope, just can obtain having good shock-resistance, good heat resistance and mobile resin combination.
The kneading unit that mixes can adopt Banbury muller, extrusion machine, kneading machine and the continuous muller etc. of known open type batch mixing with internal mixer and closed.This wherein preferably uses the device of closed, and has been preferably in to mix in the inert gas atmosphere such as nitrogen, carbon dioxide gas and kneads.When the transformation period of the used organo-peroxide that mixes was discontented with one minute, its temperature of mixing was generally at 150～280 ℃, preferably at 170～240 ℃; Its time also can be 1～20 minute, preferably at 3～10 minutes.
Among the present invention, when carrying out partial cross-linked processing with aforementioned organo-peroxide, can add such as Sulfur, the P-quininie dioxime, P, P '-dibenzoyl quininie dioxime, N-methyl-N, the 4-dinitrosoaniline, oil of mirbane, diphenylguanidine, TriMethylolPropane(TMP)-N, N '-m-phenylene dimaleimide and so on keep oxide compound crosslinking coagent or Vinylstyrene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, the polyfunctional methacrylate monomer of allyl methyl acrylate and so on, the multifunctional vinyl monomer of vinyl butyrate or stearic acid vinyl ester and so on.Owing to added above these compounds, therefore can expect to obtain evenly and the demulcent crosslinking reaction.If particularly use Vinylstyrene among the present invention, then not only owing to can make the reaction easy handling, has good intermiscibility with ethylene series rubber and olefin series plastic as above-mentioned object being treated main component, and owing to have the effect that to dissolve organo-peroxide, played the effect of superoxide dispersion agent, therefore crosslinked effect is very even after the thermal treatment, can obtain the composition of mobile and balance of physical properties.Among the present invention, this crosslinking coagent or polyfunctional vinyl monomer be for whole handled things, and its add-on can be 0.1～2%, preferably at 0.3～1%(weight percent) scope in.Because crosslinking coagent or the monomeric add-on of polyfunctional vinyl be in above-mentioned scope, so resultant composition has good shock-resistance, to add the thermal hysteresis change in physical in man-hour also very little.
In addition, in order to quicken the decomposition of organo-peroxide, also can use following decomposition accelerating agent: triethylamine, tributylamine, 2,4, the decomposition accelerating agent of the tertiary amine of 6-three (dimethylamine) phenol etc. and the naphthenate of aluminium, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead and mercury etc. etc.
The above-mentioned process of kneading of mixing is preferably in the closed-type device of inert atmospheres such as nitrogen or carbon dioxide gas and carries out, and its temperature is the temperature of transformation period less than in the time of 1 minute of used organo-peroxide, is generally 150～280 ℃, is preferably in 170～240 ℃; The time of kneading was generally 1～20 minute, preferably 1～10 minute; In addition, added shearing force, generally selecting velocity of shear is 10～10
4/ second, preferably 10
2～10
3/ second.
Internal mixer, intensive mixer that kneading unit can be used with batch mixing, for example: Banbury closed muller, kneading machine, single screw rod or twin-screw extruder etc., preferably hermetic type.
Owing to be under the condition that above-mentioned organo-peroxide exists, to carry out dynamic thermal treatment and carry out partial cross-linkedly,, thereby obtained the polyolefin elastomerics (a) of graft modification simultaneously also owing to there is composition (ⅲ) to exist.
In addition, it is partial cross-linked that graft-modified polyolefin based elastomers of the present invention (a) is carried out, be meant measure with following method, gel content more than 20%, comparatively ideal be 20～99.5%, it would be desirable and under 45～98% range of condition, carry out.
The mensuration of gel content
Weighing thermoplastic elastomer sample 100mg, put into encloses container after being cut into the thin slice of 0.5mm * 0.5mm * 0.5mm, in the hexanaphthene of 23 ℃ 30ml, soak after 48 hours, sample is taken out be placed on the filter paper again, drying is 72 hours under the room temperature, till it becomes constant.
In the weight of above-mentioned dry residue, cut the weight of all hexanaphthene insoluble compositions (fibrous stopping composition, stopping composition, pigment etc.) beyond the component of polymer and hexanaphthene, soak before the weight of olefin series plastic composition in the sample, surplus as " final weight (Y) of process revisal ".
In addition, the weight of peroxide crosslinking type ethylene series interpolymer rubber in the sample (that is, from the weight of sample, cut the weight of hexanaphthene soluble components (for example: mineral oil, softening agent and olefin series plastic composition) beyond the peroxide crosslinking type ethylene series interpolymer rubber and the hexanaphthene insoluble composition (fibrous stopping composition, stopping composition, pigment etc.) beyond the component of polymer after the surplus weight of institute) as " passing through the initial weight (X) of revisal.
Gel content can be obtained by following formula.
Gel content (weight percent)
=(through the final weight (Y) of revisal)/(through the initial weight (X) of revisal) * 100
Polymeric amide (b)
Polymeric amide of the present invention (b) is by hexanediamine, decamethylene diamine, ten dimethylene diamines, 2,2,4 or 2,2,4-trimethylammonium hexanediamine, 1,3 or 1, two (amino methyl) hexanaphthenes of 4-, two-(right-bis (aminocyclohexyl) methane) ,-or the polycondensation of the dicarboxylic acid of aliphatics such as aliphatics, alicyclic, aromatic diamines and hexanodioic acid, suberic acid, sebacic acid, cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid such as right-xylyene diamine, alicyclic, aromatic series etc. after the polymeric amide that obtains; The polymeric amide that is condensed into by aminocarboxylic acids such as the amino undecanoic acids of epsilon-amino caproic acid, 11-; Polymeric amide that is condensed into by aminocarboxylic acids such as ε-Ji Neixianan, omega-lauric lactams or the polymeric amide of forming by above-mentioned these composition polymerizations, the mixture of polymeric amide.Can enumerate as follows particularly: nylon 6, nylon 66, NYLON610, nylon 9, Ni Long11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11 etc.For the thermoplastic resin composition, nylon 6 wherein and nylon 66 are being best aspect physical strength and the thermotolerance.
With modified polyolefin based elastomers (a) and polymeric amide (b) blended method; can enumerate as follows: mix well mixed once such as machine, screw muller, cylinder muller through closed muller, V-type after, under the temperature more than the polymeric amide melting point again through the melting mixing of single-screw extrusion machine, twin-screw extruder, kneading machine, Banbury muller and the method for carrying out granulation or pulverizing.
Thermoplastic resin composition (1)
Thermoplastic resin composition's of the present invention optimum implementation (1) is mixed above-mentioned graft-modified polyolefin based elastomers (a) and polymeric amide (b) and is obtained in following ratio: (a) for greater than 50～95, preferably 60～90, (b) be 50～less than 50, preferably 10～, the 40(weight basis).
Formed modified polyolefin based thermoplastic elastomerics with α such as MALEIC ANHYDRIDE, β unsaturated carboxylic acid or derivatives thereof or unsaturated epoxy monomer through graft modification, mixed interface formed by this elastomerics and polymeric amide, two kinds of compositions of resin combination has been reinforced significantly, so this resin combination is all obtaining satisfied effect aspect oil-proofness, heat-resistant aging and the physical strength.Thereby it is widely used in trolley part (corrugated tube, tube, interior dress sheet material, splash pan etc.), industrial part (pressure piping, seal washer, barrier film etc.), electric mechanical part and material of construction etc.
Thermoplastic resin composition (2)
Being suitable for another embodiment of the present invention (2) mixes above-mentioned graft-modified polyolefin based elastomers (a) and polymeric amide (b) and obtains with following ratio: (a) be 5～50, preferably 10～30, (b) be 95～50,90～70(weight basis preferably).
Above-mentioned resulting thermoplastic resin composition is all good aspect rigidity, shock strength, flowability and thermotolerance.
Composition of the present invention, particularly as impact resistance resin, after various known method such as available injection molding, extrusion molding, compressed moulding, slush molding and foaming are carried out forming process, be widely used for coating material, trolley part, electrical component, hood and the ski boots etc. of pipe, pipe.
In the composition for thermoplastic elastomer of the present invention, the content of composition (ⅰ) and composition (ⅱ) is measured than available dsc (D.S.C method) and/or infrared absorption spectroscopy; The content useable solvents extraction process of composition (ⅳ) and composition (V) (measure by soxhlet extraction method (solvent: acetone)) and/or infrared absorption spectroscopy; The content of grafted composition (ⅲ) is measured with infrared absorption spectroscopy or chemical analysis.
Embodiment 1
In nitrogen atmosphere, be that 70 mol %, iodine number are 12, mooney viscosity ML with ethylene content with the Banbury muller
1+4(100 ℃) are 120 ethylene, propylene ethylidene norbornene interpolymer rubber [being designated hereinafter simply as: EPDM(1)] 80 parts by weight, MFR(ASTMD1238-65T, 230 ℃) be 13, density is 0.91g/cm
3Polypropylene (be designated hereinafter simply as: PP) 20 parts by weight, after mixing 5 minutes under 180 ℃, make it pass roll and become sheet, be cut into square resin material grain piece with slicing machine again, and then with the closed muller with square resin particle piece and 1,3-is two-(tert-butyl peroxide sec.-propyl) benzene [being designated hereinafter simply as: superoxide (A)] 0.3 parts by weight, (be designated hereinafter simply as: DVB) (be designated hereinafter simply as: MAH) 0.5 parts by weight mix divinylbenzene for 0.5 parts by weight, MALEIC ANHYDRIDE.Then in nitrogen atmosphere, be that the single-screw extrusion machine of 50mm is extruded said mixture with the L/D=30 screw diameter under 220 ℃, thereby made graft-modified polyolefin based elastomers (a).Determine the gel content of the interpolymer rubber in the modified polyolefin based elastomers (a) with aforesaid method, measured value is shown in table 1.
Then, with these modified polyolefin based elastomers (a) 85 weight parts and polymeric amide (ェ ニ チ ヵ system, nylon 6A1030BRF) 15 weight parts,, in nitrogen atmosphere, extrude under 250 ℃ with the single shaft extrusion machine of L/D=30, screw diameter 50mm.The composition for thermoplastic elastomer that obtains 250 ℃ of lower compression moulding, is made the sheet stock that physical property measurement is used, measure following rerum natura.It the results are shown in table 1.
Oil-proofness: Δ V%, according to JISK6301, analyte immersed in 50 ℃ the JIS3 oil 7 days, measure the volume increment rate of dipping back before with respect to dipping) (percentage).
Intensity: T
BKgf/cm
2,, measure analyte at 200mm/min according to JISK6301.The tensile strength of breaking point under the draw speed.
Flexibility: twisting strength, kgf/cm
2, according to ASTM D1043.
Formability: MFR, the g/10 branch, according to ASTM D1238,230 ℃, 2.16kg.
Thermal ageing: A
R(E
R) %, according to JISK6310, analyte is put into 135 ℃ weatherometer (ギ ヤ one ォ one プ Application) 7 days, measure ratio (conservation rate per-cent) for the breaking point elongation before aging.
Comparative example 1
Except the add-on of MALEIC ANHYDRIDE was zero this point, other were all undertaken by embodiment 1.
Embodiment 2
Except the add-on of DVB is zero, modified olefin based elastomers (a) is that 70 parts by weight, polymeric amide (b) are 30 parts by weight, other are all undertaken by embodiment 1.
Embodiment 3
Is 70 mol % with the closed muller with ethylene content, and iodine number is 12, mooney viscosity ML
1+4(100 ℃) are that 120 granular resin material ethylene, propylene ethylidene norbornene interpolymer rubber [being designated hereinafter simply as: EPDM(2)] 80 parts by weight, PP20 parts by weight, superoxide (A) 0.3 parts by weight, MAH0.5 parts by weight and DVB0.5 parts by weight mix.Then, in nitrogen atmosphere, under 220 ℃, be that the twin-screw extruder of 53mm is made modified polyolefin based elastomers (a) with said mixture with L/D=44, screw diameter.Then, except that modified polyolefin based elastomers (a) is that 55 parts by weight, polymeric amide are 45 parts by weight, other are all undertaken by embodiment 1.
Embodiment 4,5, comparative example 2
The add-on of superoxide (A) is respectively 0.6 parts by weight, 1 parts by weight, 1.5 parts by weight, and except the add-on of modified polyolefin based elastomers (a), polymeric amide (b) was as shown in table 1, other were all undertaken by embodiment 1.
Embodiment 6,7,8,9, comparative example 3
Except that EPDM(1) and the add-on of PP as shown in table 1, other are all undertaken by embodiment 3.
Embodiment 10
When making modified polyolefin based elastomers (a), except (エ ッ ソ makes with isoprene-isobutylene rubber, II R-065, degree of unsaturation be 0.8 mol %, hereinafter to be referred as: II R) and paraffin series technical oil and modified polyolefin based elastomers (a) and polymeric amide (b) join EPDM(1 by the add-on shown in the table 1) and PP in go outside, other are all undertaken by embodiment 1.
Embodiment 11
Except the MAH0.5 parts by weight being changed into glycidyl methacrylate 0.5 parts by weight, other are all undertaken by embodiment 10.
Embodiment 12,14
Except EPDM(1), the add-on of PP, II R, paraffin series technical oil, MAH, modified polyolefin based elastomers (a) and polymeric amide (b) as shown in table 1, other are all undertaken by embodiment 10.
Embodiment 13,15
Except that EPDM(1), PP, II R, paraffin series technical oil, glycidyl methacrylate, (the add-on of a, polymeric amide (b) was as shown in table 1, other were all undertaken by embodiment 11 the modified polyolefin based elastomers.
Embodiment 16
In nitrogen atmosphere, 250 ℃ down with L/D=30, screw diameter be the single-screw extrusion machine of 50mm to extrude the graft-modified polyolefin based elastomers (a) that the method by embodiment 1 produces be that 20 parts by weight and polymeric amide (6A1030BRF) they are the mixture of 80 parts by weight, can obtain resin combination based on polymeric amide (b).
Make composition dries then, use single-lead-screw extruding briquetting machine (design temperature is that 240 ℃, metal pattern temperature are 80 ℃ for model: IS-22P, the machinofacture of card sesame) to make test piece again, and measure its physical properties as follows.
＜rigidity 〉
Pliability test: according to ASTM D 790
Specimen size: 127 * 12.7 * 3.2mm
Rate of bending: 5mm/min
Obtain crooked elastic rate (FM:kg/cm
2) and stress in bending (FS:kg/cm
2).
＜intensity 〉
Tension test: according to ASTM D 638
Specimen size is pressed ASTM IV type, and thickness is 3.2mm.
Draw speed: 50mm/min
Obtain yield point stress (YS:kg/cm
2) and breaking point drawing force (YS:kg/cm
2).
＜shock strength 〉
Izod impact test: according to ASTM D 256
Specimen size: thick 3mm, band breach.
＜flowability 〉
Fusion plastic flow momentum test:,, measure under the 2.16kg condition at 230 ℃ according to ASTM D 1238.
Comparative example 4
Except that the MALEIC ANHYDRIDE add-on is that other are all undertaken by embodiment 16 zero.
Embodiment 17
Except that the add-on of DVB is zero, the add-on of modified polyolefin based elastomers (a) is 35 parts by weight, polymeric amide (b) add-on is 65 parts by weight, other are all undertaken by embodiment 16.
Embodiment 18
Except that the add-on of superoxide (A) is that 0.6 parts by weight, MAH are that the add-on of 2 parts by weight and the modified polyolefin based elastomers (a) that produced by the method for embodiment 3 is that 20 parts by weight, polymeric amide (b) are 80 parts by weight, other are all undertaken by embodiment 16.
Embodiment 19
Except that the add-on of superoxide (A) is that other were all undertaken by embodiment 18 add-on of 1 parts by weight, MAH and modified polyolefin based elastomers (a), polymeric amide (b) was pressed shown in the table 2.
Comparative example 5
Except that EPDM(1) add-on be that 100 parts by weight, superoxide (A) they are 0.05 parts by weight and do not add PP and the DVB that other are all undertaken by embodiment 16.
Embodiment 20,21, comparative example 6
Except that EPDM(1), the add-on of PP as shown in table 2, other are all undertaken by embodiment 18.
Embodiment 22
When making modified polyolefin based elastomers (a), except that II R and paraffin series technical oil and modified polyolefin based elastomers (a) and polymeric amide (b) are joined EPDM(1 by the amount shown in the table 2) and PP in, other are all undertaken by embodiment 1.
Embodiment 23
Except using glycidyl methacrylate 0.5 parts by weight to replace the MAH0.5 parts by weight, other are all undertaken by embodiment 22.
Embodiment 24
Except that EPDM(1), the add-on of PP, II R, paraffin series technical oil, MAH, modified polyolefine elastomer (a) and polymeric amide (b) be shown in the table 2, other are all undertaken by embodiment 22.
Embodiment 25
Except that EPDM(1), PP, II R, paraffin series technical oil, glycidyl methacrylate, (the add-on of a, polymeric amide (b) was as shown in table 2, other were all undertaken by embodiment 23 the modified polyolefin based elastomers.
Embodiment 26,27
Except that EPDM(1), PP, II R, oil be the add-on of technical oil, hydroxypropyl methacrylate, modified polyolefin based elastomers (a) and polymeric amide (b) as shown in table 2, other are all undertaken by embodiment 23.
Embodiment 28
Except that MALEIC ANHYDRIDE being changed into hydroxypropyl methacrylate, other are all undertaken by embodiment 10.
Embodiment 29
Except that MALEIC ANHYDRIDE being changed into hydroxypropyl methacrylate, other are all undertaken by embodiment 14.
Claims (3)
1, a kind of thermoplastic resin composition is characterized in that, will contain
(i) peroxide crosslinking type ethylene series copolymer rubber 95-10 weight part,
(ii) olefin series plastic 5-90 weight part, at this, when selecting above-mentioned binary, must make (i)+(ii)=100 weight part
(iii) unsaturated carboxylic acid or derivatives thereof, unsaturated epoxy monomer or unsaturated carboxylic monomer 0.01-10 weight part, mixture, be equivalent to composition (i), (ii) and (iii) under the existence of the organo-peroxide of gross weight 0.05-3%, carry out dynamic thermal treatment and the poly-hydrocarbon system elastomerics (a) of partial cross-linked graft modification takes place, with polymeric amide (b), in weight basis, cooperate in following ratio
(a) greater than 50 to 95,
(b) 5 to below 50.
2, thermoplastic resin composition according to claim 1, it is characterized in that this graft-modified polyolefin based elastomers (a) also contains (IV) and/or (V) composition, its amount is respectively with respect to described (ⅰ) composition with (ⅱ) when the composition total amount is 100 weight parts:
(ⅳ) superoxide non-crosslinked type rubber-like substance 0-100 weight part, and/or,
(V) mineral oil softener 0-200 weight part.
3, combinations of thermoplastic resins according to claim 1 is characterized in that the consumption of organo-peroxide is equivalent to composition (ⅰ), (ⅱ) and (ⅲ) 0.1-1% of gross weight.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP256871/86 | 1986-10-30 | ||
| JP25687186 | 1986-10-30 | ||
| JP118942/87 | 1987-05-18 | ||
| JP11894287 | 1987-05-18 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93101490A Division CN1048030C (en) | 1986-10-30 | 1993-02-01 | Thermoplastic resin compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87107381A CN87107381A (en) | 1988-06-01 |
| CN1030459C true CN1030459C (en) | 1995-12-06 |
Family
ID=26456771
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107381A Expired - Fee Related CN1030459C (en) | 1986-10-30 | 1987-10-30 | Composition of thermoplastic resin |
| CN93101490A Expired - Fee Related CN1048030C (en) | 1986-10-30 | 1993-02-01 | Thermoplastic resin compositions |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93101490A Expired - Fee Related CN1048030C (en) | 1986-10-30 | 1993-02-01 | Thermoplastic resin compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0266221B1 (en) |
| KR (1) | KR910005572B1 (en) |
| CN (2) | CN1030459C (en) |
| AU (1) | AU599715B2 (en) |
| CA (1) | CA1299791C (en) |
| DE (1) | DE3789275T2 (en) |
| MY (1) | MY102988A (en) |
| NZ (1) | NZ222384A (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0274744A3 (en) * | 1987-01-16 | 1989-12-06 | General Electric Company | Epoxy containing impact modifiers for thermoplastic resins |
| JPH0277458A (en) * | 1988-06-17 | 1990-03-16 | Sumitomo Chem Co Ltd | Ethylene-alpha-olefin copolymer-based vulcanized rubber composition |
| US5212238A (en) * | 1988-12-22 | 1993-05-18 | Ferro Corporation | Toughened compositions of polyamide and functionalized rubber block or graft copolymers |
| MY105557A (en) * | 1989-05-12 | 1994-10-31 | Mitsui Petrochemical Ind | Thermoplastic resin composition and use thereof. |
| IT1246980B (en) * | 1990-07-12 | 1994-12-12 | Montedipe Srl | THERMOPLASTIC COMPOSITIONS BASED ON A SCRATCHED AROMATIC VINYL COPOLYMER AND A POLYAMIDE |
| US5574105A (en) * | 1995-05-12 | 1996-11-12 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers having improved high temperature performance |
| JP3168450B2 (en) * | 1995-09-29 | 2001-05-21 | 住友化学工業株式会社 | Method for producing thermoplastic elastomer composition |
| CN1320059C (en) * | 2002-12-27 | 2007-06-06 | 汎塑料株式会社 | Amorphous wholly aromatic polyester amide composition |
| US7268185B2 (en) * | 2003-09-24 | 2007-09-11 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition and its injection molded article |
| CN100547029C (en) * | 2007-04-20 | 2009-10-07 | 常熟佳发化学有限责任公司 | A kind of unsaturated resin composition, and preparation method thereof with its using method |
| DE102007043972B4 (en) | 2007-09-11 | 2009-09-17 | Kometra Kunststoff-Modifikatoren Und -Additiv Gmbh | Process for the preparation of carboxylated ethylene polymer blends |
| DE102008019804B4 (en) | 2008-04-15 | 2019-11-14 | Byk-Chemie Gmbh | Functionalized high adhesion ethylene polymers and process for their preparation |
| EP2574635A1 (en) * | 2011-09-28 | 2013-04-03 | Lanxess Inc. | Process for continuous production of halogen-free thermoplastic elastomer compositions |
| TWI644987B (en) * | 2012-08-10 | 2018-12-21 | 日商住友橡膠工業股份有限公司 | Medical rubber |
| WO2014146773A1 (en) | 2013-03-20 | 2014-09-25 | Byk Kometra Gmbh | Method for producing functionalized thermoplastic elastomers |
| CN103951969A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Polyamide toughening material and preparation method thereof |
| CN108299822A (en) * | 2017-12-27 | 2018-07-20 | 上海普利特复合材料股份有限公司 | A kind of Long Glass Fiber Reinforced Pa PA66 composite material and preparation methods of the hot high-temerature creep of oil resistant |
| KR102126912B1 (en) * | 2019-01-16 | 2020-06-26 | 한국기술교육대학교 산학협력단 | Polyolefin/polyamide resin composition having improved impact strength |
| CN116606544B (en) * | 2023-04-03 | 2024-05-03 | 昆明鼎骏塑业有限公司 | Heat-resistant impact-resistant polyamide plastic and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4212878A (en) * | 1978-01-26 | 1980-07-15 | The Upjohn Company | Phenylacetamide derivative analgesics |
| JPS55165952A (en) * | 1979-06-14 | 1980-12-24 | Unitika Ltd | Polyamide composition |
| JPH0674298B2 (en) * | 1983-02-14 | 1994-09-21 | 三菱化成株式会社 | Resin composition |
| US4594386A (en) * | 1983-08-15 | 1986-06-10 | Copolymer Rubber & Chemical Corporation | Polyamide grafted EPM blend |
| EP0209566A1 (en) * | 1985-01-11 | 1987-01-28 | COPOLYMER RUBBER & CHEMICAL CORPORATION | Polyesters having improved impact strength |
| KR960013123B1 (en) * | 1986-09-25 | 1996-09-30 | 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 | Impact resistant polymer composition and process thereof |
-
1987
- 1987-10-30 AU AU80555/87A patent/AU599715B2/en not_active Ceased
- 1987-10-30 EP EP87309642A patent/EP0266221B1/en not_active Expired - Lifetime
- 1987-10-30 KR KR1019870012116A patent/KR910005572B1/en not_active IP Right Cessation
- 1987-10-30 DE DE3789275T patent/DE3789275T2/en not_active Expired - Lifetime
- 1987-10-30 CN CN87107381A patent/CN1030459C/en not_active Expired - Fee Related
- 1987-10-30 MY MYPI87002997A patent/MY102988A/en unknown
- 1987-10-30 NZ NZ222384A patent/NZ222384A/en unknown
- 1987-10-30 CA CA000550669A patent/CA1299791C/en not_active Expired - Fee Related
-
1993
- 1993-02-01 CN CN93101490A patent/CN1048030C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU599715B2 (en) | 1990-07-26 |
| KR880014027A (en) | 1988-12-22 |
| AU8055587A (en) | 1988-05-05 |
| CA1299791C (en) | 1992-04-28 |
| MY102988A (en) | 1993-03-31 |
| DE3789275T2 (en) | 1994-06-09 |
| EP0266221A2 (en) | 1988-05-04 |
| EP0266221A3 (en) | 1989-09-27 |
| KR910005572B1 (en) | 1991-07-31 |
| EP0266221B1 (en) | 1994-03-09 |
| CN1048030C (en) | 2000-01-05 |
| CN87107381A (en) | 1988-06-01 |
| CN1074456A (en) | 1993-07-21 |
| DE3789275D1 (en) | 1994-04-14 |
| NZ222384A (en) | 1990-07-26 |
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